WO2015147279A1 - Pile rechargeable entièrement solide, composition d'électrolyte solide et feuille d'électrode de pile utilisée pour celle-ci, et procédé de fabrication d'une feuille d'électrode de pile et d'une pile rechargeable entièrement solide - Google Patents

Pile rechargeable entièrement solide, composition d'électrolyte solide et feuille d'électrode de pile utilisée pour celle-ci, et procédé de fabrication d'une feuille d'électrode de pile et d'une pile rechargeable entièrement solide Download PDF

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WO2015147279A1
WO2015147279A1 PCT/JP2015/059677 JP2015059677W WO2015147279A1 WO 2015147279 A1 WO2015147279 A1 WO 2015147279A1 JP 2015059677 W JP2015059677 W JP 2015059677W WO 2015147279 A1 WO2015147279 A1 WO 2015147279A1
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solid electrolyte
group
secondary battery
solid
active material
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PCT/JP2015/059677
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Japanese (ja)
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宏顕 望月
智則 三村
雅臣 牧野
目黒　克彦
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富士フイルム株式会社
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Publication of WO2015147279A1 publication Critical patent/WO2015147279A1/fr
Priority to US15/272,644 priority Critical patent/US10297859B2/en

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    • C08B3/00—Preparation of cellulose esters of organic acids
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/139—Processes of manufacture
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Definitions

  • the present invention relates to an all-solid secondary battery, a solid electrolyte composition used therefor, and an electrode sheet for a battery, and an electrode sheet for a battery and a method for producing an all-solid secondary battery.
  • the inorganic solid electrolyte exhibits higher ionic conductivity than the polymer electrolyte.
  • a further advantage of the all-solid-state secondary battery is that it is suitable for increasing the energy density by stacking electrodes. Specifically, a battery having a structure in which an electrode and an electrolyte are directly arranged in series can be obtained. At this time, since the metal package for sealing the battery cell, the copper wire and the bus bar for connecting the battery cell can be omitted, the energy density of the battery is greatly increased. In addition, good compatibility with the positive electrode material capable of increasing the potential is also mentioned as an advantage.
  • Non-patent Document 1 Developed as a next-generation lithium ion secondary battery due to the above-described advantages, it has been vigorously developed (Non-patent Document 1).
  • an inorganic all-solid secondary battery has a disadvantage because the electrolyte is a hard solid. For example, the interface resistance between solid particles is increased.
  • Patent Document 1 uses a surfactant having a polyoxyethylene chain.
  • Patent Document 2 discloses the use of a hydrogenated butadiene copolymer.
  • Patent Document 3 discloses a lithium ion secondary battery in which a gap between an active material and an oxide-based inorganic solid electrolyte is impregnated with sulfolane.
  • the present invention provides an all-solid-state secondary battery that achieves high ionic conductivity regardless of the pressurization of the active material layer and the inorganic solid electrolyte layer, and further realizes good binding properties of the material. It aims at providing the manufacturing method of a secondary battery, the solid electrolyte composition used for this, an electrode sheet for batteries, and an all-solid-state secondary battery.
  • An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the inorganic solid electrolyte layer
  • the all-solid-state secondary battery containing the inorganic solid electrolyte which has the conductivity of the ion of the metal which belongs to periodic table 1st group or 2nd group, and a cellulose polymer.
  • L 2 , L 3 and L 6 each independently represent a single bond or a divalent linking group.
  • X 2 , X 3 , and X 6 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group containing a hetero atom having 1 to 30 carbon atoms.
  • L 2 , L 3 , and L 6 each independently represent a single bond, a carbonyl group, a carbonyloxy group, or an amide group.
  • L 2 , L 3 and L 6 each independently represent a single bond or a divalent linking group.
  • X 2 , X 3 , and X 6 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group containing a hetero atom having 1 to 30 carbon atoms.
  • At least one of X 2 , X 3 and X 6 is a hydrocarbon group having 3 or more carbon atoms or a hydrocarbon group containing 1 to 30 carbon atoms in [11] or [12]
  • each substitution may be the same as or different from each other. Further, when a plurality of substituents and the like are close to each other, they may be bonded to each other or condensed to form a ring.
  • the all-solid-state secondary battery of the present invention achieves high ionic conductivity regardless of the pressure applied between the active material layer and the inorganic solid electrolyte layer, and further has excellent material binding properties. According to the solid electrolyte composition, the battery electrode sheet, and the production method of the present invention, an all-solid secondary battery that exhibits the above-described excellent performance can be suitably produced.
  • FIG. 1 is a cross-sectional view schematically showing an all solid lithium ion secondary battery according to a preferred embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing a test apparatus used in the examples.
  • the all-solid-state secondary battery of the present invention includes a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer, and any one of the layers contains an ion conductive inorganic solid electrolyte and a cellulose polymer.
  • FIG. 1 is a cross-sectional view schematically showing an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid-state secondary battery 10 of the present embodiment includes a negative electrode current collector 1, a negative electrode active material layer 2, an inorganic solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in that order as viewed from the negative electrode side. Have in.
  • Each layer is in contact with each other and has a laminated structure.
  • the solid electrolyte composition of the present invention is preferably used as a constituent material of the negative electrode active material layer, the positive electrode active material layer or the inorganic solid electrolyte layer, and among them, the inorganic solid electrolyte layer, the positive electrode active material layer, and the negative electrode active material layer. It is preferable to use as all constituent materials.
  • the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as an “active material layer”.
  • the inorganic solid electrolyte layer may be referred to as “solid electrolyte layer” or “electrolyte layer”.
  • the thicknesses of the positive electrode active material layer 4 and the negative electrode active material layer 2 can be determined according to the target battery capacity. In consideration of general element dimensions, it is preferably 1 ⁇ m or more, and more preferably 3 ⁇ m or more. As an upper limit, it is preferable that it is 1000 micrometers or less, and it is more preferable that it is 400 micrometers or less.
  • the inorganic solid electrolyte layer 3 is desirably as thin as possible while preventing a short circuit between the positive and negative electrodes. Furthermore, it is preferable that the effect of the present invention is remarkably exhibited. Specifically, it is preferably 1 ⁇ m or more, and more preferably 3 ⁇ m.
  • a laminate including a current collector, an active material layer, and a solid electrolyte layer is referred to as an “all-solid secondary battery”.
  • the secondary battery electrode sheet may be housed in a casing (case) to be an all-solid secondary battery (for example, a coin battery, a laminate battery, or the like).
  • the solid electrolyte composition of the present invention refers to a composition containing an inorganic solid electrolyte, and is a material that forms at least one of an inorganic solid electrolyte layer, a positive electrode active material layer, and a negative electrode active material layer of an all-solid secondary battery. Used as The solid electrolyte composition is not limited to a solid, and may be liquid or pasty.
  • An inorganic solid electrolyte is an inorganic solid electrolyte.
  • solid electrolyte means a solid electrolyte capable of moving ions therein.
  • the inorganic solid electrolyte may be referred to as an ion conductive inorganic solid electrolyte in consideration of the distinction from the electrolyte salt (supporting electrolyte) described later.
  • the ionic conductivity of the inorganic solid electrolyte is not particularly limited, but is preferably 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 1 ⁇ 10 ⁇ 5 S / cm or more in lithium ions. More preferably, it is 10 ⁇ 4 S / cm or more, and particularly preferably 1 ⁇ 10 ⁇ 3 S / cm or more. There is no particular upper limit, but 1 S / cm or less is practical. Unless otherwise specified, the ion conductivity measurement method is based on the non-pressurized conditions measured in Examples described later.
  • inorganic solid electrolytes do not contain organic compounds such as polymer compounds and complex salts as electrolytes
  • organic solid electrolytes polymer electrolytes typified by PEO (polyethylene oxide), organic electrolyte salts typified by LiTFSI, etc.
  • the inorganic solid electrolyte is a non-dissociable solid in a steady state, it does not dissociate or release into cations and anions even in the liquid.
  • inorganic electrolyte salts LiPF 6 , LiBF 4 , LiFSI, LiCl, etc.
  • the inorganic solid electrolyte has conductivity of metal ions (preferably lithium ions) belonging to Group 1 or Group 2 of the periodic table, but does not have electronic conductivity.
  • the electrolyte layer or the active material layer contains a metal ion (preferably lithium ion) conductive inorganic solid electrolyte belonging to Group 1 or Group 2 of the Periodic Table.
  • a metal ion preferably lithium ion
  • the inorganic solid electrolyte a solid electrolyte material applied to this type of product can be appropriately selected and used.
  • Typical examples of the inorganic solid electrolyte include (i) sulfide-based inorganic solid electrolyte (sometimes referred to as sulfide solid electrolyte) and (ii) oxide-based inorganic solid electrolyte (sometimes referred to as oxide solid electrolyte). As mentioned.
  • a sulfide solid electrolyte contains sulfur (S), has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and has electronic insulation. Those having properties are preferred.
  • a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula (A) can be mentioned.
  • L a1 M b1 P c1 S d1 A e1 (A) (In the formula, L represents an element selected from Li, Na, and K, and Li is preferable.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge.
  • E1 represents the composition ratio of each element, and a1: b1: c1: d1: e1 satisfies 1 to 12: 0 to 1: 1: 2 to 12: 0 to 5. a1 is more preferably 1 to 9 1.5 to 4 is more preferable, b1 is preferably 0 to 0.5, d1 is further preferably 3 to 7, more preferably 3.25 to 4.5, and e1 is further preferably 0 to 3. 0 to 1 are more preferable.)
  • the composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based solid electrolyte as described below.
  • the sulfide-based solid electrolyte may be amorphous (glass) or crystallized (glass ceramics), or only part of it may be crystallized.
  • the ratio of Li 2 S to P 2 S 5 in the Li—PS system glass and the Li—PS system glass ceramic is a molar ratio of Li 2 S: P 2 S 5 , preferably 65:35 to 85:15, more preferably 68:32 to 75:25.
  • the lithium ion conductivity can be increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no upper limit, it is practical that it is 1 ⁇ 10 ⁇ 1 or less.
  • the compound include those using a raw material composition containing, for example, Li 2 S and a sulfide of an element belonging to Group 13 to Group 15.
  • Li 2 S—P 2 S 5 Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 O—P 2 S 5 , Li 2 S—LiBr—P 2 S 5 Li 2 S—Li 2 O—P 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 —P 2 O 5 , Li 2 SP—P 2 S 5 —SiS 2 , Li 2 S—P 2 S 5 —SnS, Li 2 S—P 2 S 5 —Al 2 S 3 , Li 2 S—GeS 2 , Li 2 S—GeS 2 —ZnS, Li 2 S—Ga 2 S 3 , Li 2 S—GeS 2 —Ga 2 S 3 , Li 2 S—GeS 2 —GeS 2
  • a crystalline and / or amorphous raw material composition comprising Li 2 S—GeS 2 —P 2 S 5 or Li 10 GeP 2 S 12 is preferred because it has high lithium ion conductivity.
  • Examples of a method for synthesizing a sulfide solid electrolyte material using such a raw material composition include an amorphization method.
  • Examples of the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
  • the sulfide solid electrolyte is more preferably one represented by the following formula (B).
  • Li l P m Sn formula (B) In the formula, l to n represent the composition ratio of each element, and l: m: n satisfies 2 to 4: 1: 3 to 10.
  • Oxide-based inorganic solid electrolyte contains oxygen (O), has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is an electron What has insulation is preferable.
  • ⁇ 4 was filled, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, nb satisfies 5 ⁇ nb ⁇ 20.) Li xc B yc M cc zc O nc (M cc is C , S, Al, Si, Ga, Ge, In, and Sn, xc satisfies 0 ⁇ xc ⁇ 5, yc satisfies 0 ⁇ yc ⁇ 1, and zc satisfies 0 ⁇ zc ⁇ 1.
  • Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON obtained by replacing a part of oxygen of lithium phosphate with nitrogen
  • LiPOD 1 LiPOD 1
  • LiA 1 ON A 1 is at least one selected from Si, B, Ge, Al, C, Ga, etc.
  • the ionic conductivity of the lithium ion conductive oxide-based inorganic solid electrolyte is preferably 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 1 ⁇ 10 ⁇ 5 S / cm or more.
  • X 10 ⁇ 5 S / cm or more is particularly preferable.
  • an oxide-based inorganic solid electrolyte Since the oxide-based inorganic solid electrolyte generally has a higher hardness, the interface resistance is likely to increase in the all-solid secondary battery. By applying the present invention, the effect becomes more prominent.
  • an oxide-based inorganic solid electrolyte and oxygen-containing groups (ether group, carbonyl group, hydroxyl group, etc.) of the following cellulose polymer act to form a more suitable adsorption state.
  • an oxide-based inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the average particle size of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less.
  • the concentration of the inorganic solid electrolyte in the solid electrolyte composition is preferably 50% by mass or more and 100% by mass in 100% by mass of the solid component when considering both the battery performance and the reduction / maintenance effect of the interface resistance. % Or more is more preferable, and 90% by mass or more is particularly preferable. As an upper limit, it is preferable that it is 99.9 mass% or less from the same viewpoint, It is more preferable that it is 99.5 mass% or less, It is especially preferable that it is 99 mass% or less. However, when used together with a positive electrode active material or a negative electrode active material to be described later, the sum is preferably in the above concentration range.
  • Cellulose polymer In the present invention, it is preferable to use a cellulose polymer as a binder for the inorganic solid electrolyte.
  • This cellulose polymer preferably has a repeating unit represented by the following formula (1).
  • L 2 , L 3 and L 6 each independently represent a single bond or a divalent linking group.
  • a divalent linking group a carbonyl group (—CO—), a carbonyloxy group (—COO—), an amide group (—CONR N —), or a combination thereof is preferable.
  • L 2 , L 3 and L 6 are preferably a single bond, a carbonyl group or an amide group.
  • RN represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms.
  • At least one of L 2 , L 3 and L 6 is preferably a divalent linking group.
  • the linking group is represented by a glucose ring on the left side and a substituent X on the right side.
  • X substituent on the right side.
  • the relationship of —O—COO—X of the glucose ring is preferable.
  • X 2 , X 3 , and X 6 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having a hetero atom having 1 to 30 carbon atoms.
  • X 2 , X 3 , and X 6 are hydrocarbon groups, it is preferably a group having a relatively large number of carbon atoms. In one embodiment thereof, the carbon number is preferably 3 to 30, and more preferably 3 to 20.
  • X 2 , X 3 , and X 6 are hydrocarbon groups, they are alkyl groups (preferably having 1 to 30 carbon atoms, more preferably 3 to 20 carbon atoms), alkenyl groups (preferably having 2 to 30 carbon atoms, More preferably 3 to 20 carbon atoms, an alkynyl group (preferably 2 to 30 carbon atoms, more preferably 3 to 20 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 22 carbon atoms). ), An aralkyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 23 carbon atoms) is preferable.
  • X 2 , X 3 , and X 6 may have an optional substituent T described later as long as a desired effect is exhibited.
  • X 2 , X 3 , and X 6 are each a hydrocarbon group having a hetero atom, a hydrocarbon group in which a hydrogen atom of the hydrocarbon group is partially or completely substituted with a halogen atom (preferably having a carbon number of 1 to 30, more preferably 3 to 20 carbon atoms), a hydrocarbon group having an ether group or a thioether group in which an oxygen atom or a sulfur atom connects carbon atoms (preferably 1 to 30 carbon atoms, more preferably 3 to 20 carbon atoms). ) Is preferred.
  • a fluoroalkyl group or an alkyleneoxy group in which a hydrogen atom is substituted with a fluorine atom.
  • the degree of halogen substitution is preferably 5% or more, more preferably 10% or more, and particularly preferably 15% or more, assuming that all the substitutable positions are substituted as 100%.
  • the upper limit is not particularly limited as long as it is 100% or less.
  • the number of intervening oxygen or sulfur is preferably 1-20, and more preferably 1-15.
  • X 2 , X 3 , and X 6 may have an optional substituent T described later as long as a desired effect is exhibited.
  • the above X 2 , X 3 , and X 6 are preferably unsubstituted, but if they have a substituent, it is preferable that they have few polar groups from the viewpoint of not improving water absorption.
  • the total substitution degree of hydroxyl groups in the cellulose polymer is preferably 0.3 or more, more preferably 1 or more, further preferably 1.5 or more, and particularly preferably 2 or more.
  • the upper limit is 3 or less.
  • the total substitution degree of hydroxyl groups is an average value of hydroxyl groups substituted per ⁇ -glucose ring unit in the cellulose polymer. Therefore, when the hydroxyl groups at the 2-position, 3-position, and 6-position of the ⁇ -glucose ring or all the hydrogen atoms thereof are substituted, the total degree of substitution of the hydroxyl groups is 3. Conversely, it is 0 if no substitution is made. Unless otherwise specified, the total substitution degree of the hydroxyl group is based on the conditions measured in Examples described later.
  • repeating unit constituting the cellulose polymer are exemplified below, but the present invention is not construed as being limited thereto.
  • surface has shown as a combination of the coupling group and substituent of Formula (1).
  • linking group L A, L B, L C and represent the subscripts A, B, and C are intended for convenience attached sequentially, 2-position of the ⁇ - glucose ring, 3-position, the 6-hydroxyl group This represents that the hydroxyl group at the 3-position on the ⁇ -glucose ring is randomly substituted regardless of the position of.
  • the linking group L A represents that the substituent X A is substituted.
  • the subscripts B and C When the hydroxyl group remains without being substituted, -LX is represented as a single bond and a hydrogen atom, and the degree of substitution is represented as DS A in this specification.
  • the cellulose polymer can be synthesized or procured by a conventional method.
  • the weight average molecular weight of the cellulose polymer is preferably 10,000 or more, more preferably 50,000 or more, and particularly preferably 100,000 or more. As an upper limit, it is preferable that it is 2,000,000 or less, and it is more preferable that it is 1,000,000 or less.
  • the weight average molecular weight of a cellulose polymer is measured by the method similar to the measuring method of the weight average molecular weight of the polymer shown by the term of the below-mentioned Example.
  • the blending amount of the cellulose polymer is preferably 0.1 parts by mass or more and 0.3 parts by mass or more with respect to 100 parts by mass of the inorganic solid electrolyte (including this when an active material is used). Is more preferable, and it is particularly preferably 1 part by mass or more.
  • the upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less.
  • the cellulose polymer in the solid content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and more preferably 1% by mass or more. Particularly preferred.
  • the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
  • the cellulose polymer may be used alone or in combination of a plurality of types. Moreover, you may use in combination with another polymer.
  • alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl A group preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like
  • a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.
  • each of the groups listed as the substituent T may be further substituted with the substituent T described above.
  • a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted.
  • an alkyl group, an alkylene group, an alkenyl group, alkenylene group, an alkynyl group, an alkynylene group group containing a hetero atom may be interposed, or a ring structure may be formed with this.
  • a hetero atom e.g., O, S, CO, NR N (R N is the same meaning as above R N Etc.
  • an aryl group, a heterocyclic group, etc. may be monocyclic or condensed and may be similarly substituted or unsubstituted.
  • the solid electrolyte composition according to the present invention may contain an electrolyte salt (supporting electrolyte).
  • the electrolyte salt is preferably a lithium salt.
  • a lithium salt usually used in this type of product is preferable, and there is no particular limitation, but for example, the following are preferable.
  • Inorganic lithium salts inorganic fluoride salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; perhalogenates such as LiClO 4 , LiBrO 4 , LiIO 4 ; inorganic chloride salts such as LiAlCl 4 etc.
  • (L-3) Oxalatoborate salt lithium bis (oxalato) borate, lithium difluorooxalatoborate and the like.
  • Rf 1 and Rf 2 each represent a perfluoroalkyl group.
  • the content of the lithium salt is preferably 0.1 parts by mass or more and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the inorganic solid electrolyte.
  • As an upper limit it is preferable that it is 10 mass parts or less, and it is more preferable that it is 5 mass parts or less.
  • an electrolyte may be used individually by 1 type, or may combine 2 or more types arbitrarily.
  • a dispersion medium in which the above components are dispersed may be used.
  • a dispersion medium When producing an all-solid secondary battery, it is preferable to add a dispersion medium to the solid electrolyte composition to make a paste from the viewpoint of uniformly coating the solid electrolyte composition to form a film.
  • the dispersion medium When forming the solid electrolyte layer of the all-solid secondary battery, the dispersion medium is removed by drying.
  • the dispersion medium include water-soluble or water-insoluble organic solvents. Specific examples include the following.
  • Alcohol compound solvent Methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl- 2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, etc.
  • Ether compound solvents (including hydroxyl group-containing ether compounds) Dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether , Diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.) Amide compound solvents N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolid
  • the dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 80 ° C. or higher at normal pressure (1 atm).
  • the upper limit is preferably 220 ° C. or lower, and more preferably 180 ° C. or lower.
  • the said dispersion medium may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the quantity of the dispersion medium in a solid electrolyte composition can be made into arbitrary quantity with the balance of the viscosity of a solid electrolyte composition, and a dry load. Generally, it is preferably 20 to 99% by mass in the solid electrolyte composition.
  • the solid electrolyte composition may contain a positive electrode active material to form a positive electrode active material layer. Thereby, it can be set as the composition for positive electrode materials. It is preferable to use a transition metal oxide for the positive electrode active material, and it is preferable to have a transition element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V). Further, mixed element M b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si , P, B, etc.) may be mixed.
  • a transition element M a one or more elements selected from Co, Ni, Fe, Mn, Cu, and V.
  • mixed element M b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si
  • transition metal oxide examples include specific transition metal oxides including those represented by any of the following formulas (MA) to (MC), or other transition metal oxides such as V 2 O 5 and MnO 2. Is mentioned.
  • the positive electrode active material a particulate positive electrode active material may be used. Specifically, a transition metal oxide capable of reversibly inserting and releasing lithium ions can be used, but the specific transition metal oxide is preferably used.
  • the transition metal oxides, oxides containing the above transition element M a is preferably exemplified.
  • a mixed element M b (preferably Al) or the like may be mixed.
  • the mixing amount is preferably 0 to 30 mol% with respect to the amount of the transition metal. That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
  • M 1 is as defined above Ma.
  • a represents 0 to 1.2 (preferably 0.2 to 1.2), and preferably 0.6 to 1.1.
  • b represents 1 to 3 and is preferably 2.
  • a part of M 1 may be substituted with the mixed element M b .
  • the transition metal oxide represented by the above formula (MA) typically has a layered rock salt structure.
  • the transition metal oxide is more preferably one represented by the following formulas.
  • g has the same meaning as a.
  • j represents 0.1 to 0.9.
  • i represents 0 to 1; However, 1-ji is 0 or more.
  • k has the same meaning as b above.
  • Specific examples of the transition metal compound include LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate) LiNi 0.85 Co 0.01 Al 0.05 O 2 (nickel cobalt aluminum acid Lithium [NCA]), LiNi 0.33 Co 0.33 Mn 0.33 O 2 (lithium nickel manganese cobaltate [NMC]), LiNi 0.5 Mn 0.5 O 2 (lithium manganese nickelate).
  • the transition metal oxide represented by the formula (MA) partially overlaps, but when represented by changing the notation, those represented by the following are also preferable examples.
  • (I) Li g Ni x Mn y Co z O 2 (x> 0.2, y> 0.2, z ⁇ 0, x + y + z 1) Representative: Li g Ni 1/3 Mn 1/3 Co 1/3 O 2 Li g Ni 1/2 Mn 1/2 O 2
  • (Ii) Li g Ni x Co y Al z O 2 (x> 0.7, y>0.1,0.1> z ⁇ 0.05, x + y + z 1) Representative: Li g Ni 0.8 Co 0.15 Al 0.05 O 2
  • M 2 is as defined above Ma.
  • c represents 0 to 2 (preferably 0.2 to 2), and preferably 0.6 to 1.5.
  • d represents 3 to 5 and is preferably 4.
  • the transition metal oxide represented by the formula (MB) is more preferably one represented by the following formulas.
  • (MB-1) Li m Mn 2 O n
  • (MB-2) Li m Mn p Al 2-p O n
  • (MB-3) Li m Mn p Ni 2-p O n
  • m is synonymous with c.
  • n is synonymous with d.
  • p represents 0-2.
  • Specific examples of the transition metal compound are LiMn 2 O 4 and LiMn 1.5 Ni 0.5 O 4 .
  • Preferred examples of the transition metal oxide represented by the formula (MB) include those represented by the following.
  • an electrode containing Ni is more preferable from the viewpoint of high capacity and high output.
  • Transition metal oxide represented by formula (MC) As the lithium-containing transition metal oxide, it is also preferable to use a lithium-containing transition metal phosphor oxide, and among them, one represented by the following formula (MC) is also preferable. Li e M 3 (PO 4 ) f ... (MC)
  • e represents 0 to 2 (preferably 0.2 to 2), and is preferably 0.5 to 1.5.
  • f represents 1 to 5, and preferably 0.5 to 2.
  • the M 3 represents one or more elements selected from V, Ti, Cr, Mn, Fe, Co, Ni, and Cu.
  • the M 3 are, in addition to the mixing element M b above, Ti, Cr, Zn, Zr, may be substituted by other metals such as Nb.
  • Specific examples include, for example, olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , cobalt phosphates such as LiCoPO 4 , and Li 3.
  • Monoclinic Nasicon type vanadium phosphate salts such as V 2 (PO 4 ) 3 (lithium vanadium phosphate) can be mentioned.
  • the a, c, g, m, and e values representing the composition of Li are values that change due to charge and discharge, and are typically evaluated as values in a stable state when Li is contained.
  • the composition of Li is shown as a specific value, but this also varies depending on the operation of the battery.
  • the average particle size of the positive electrode active material is not particularly limited, but is preferably 0.1 ⁇ m to 50 ⁇ m.
  • an ordinary pulverizer or classifier may be used.
  • the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the concentration of the positive electrode active material is not particularly limited, but is preferably 20 to 90% by mass, and more preferably 40 to 80% by mass in 100% by mass of the solid component in the solid electrolyte composition.
  • the positive electrode active materials may be used alone or in combination of two or more.
  • the material is not particularly limited, and is a carbonaceous material, a metal oxide such as tin oxide or silicon oxide, a metal composite oxide, a lithium alloy such as lithium alone or a lithium aluminum alloy, and an alloy with lithium such as Sn or Si. Examples thereof include metals that can be formed. Of these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability. In addition, the metal composite oxide is preferably capable of inserting and extracting lithium.
  • the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • Examples thereof include carbonaceous materials obtained by baking various synthetic resins such as artificial pitches such as petroleum pitch, natural graphite, and vapor-grown graphite, and PAN-based resins and furfuryl alcohol resins.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, mesophase micro
  • Examples thereof include spheres, graphite whiskers, and flat graphite.
  • carbonaceous materials can be divided into non-graphitizable carbon materials and graphite-based carbon materials depending on the degree of graphitization.
  • the carbonaceous material preferably has a face spacing, density, and crystallite size described in JP-A-62-222066, JP-A-2-6856, and 3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, or the like is used. You can also.
  • an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • amorphous metal oxides and chalcogenides are more preferable, and elements in groups 13 (IIIB) to 15 (VB) of the periodic table are preferable.
  • oxides and chalcogenides composed of one kind of Al, Ga, Si, Sn, Ge, Pb, Sb, Bi or a combination of two or more kinds thereof.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , such as SnSiS 3 may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the average particle size of the negative electrode active material is preferably 0.1 ⁇ m to 60 ⁇ m.
  • a pulverizer or a classifier is used.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used.
  • wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the chemical formula of the compound obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method, and from a mass difference between powders before and after firing as a simple method.
  • ICP inductively coupled plasma
  • Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge include carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, lithium A metal that can be alloyed with is preferable.
  • the negative electrode active material preferably contains a titanium atom. More specifically, since Li 4 Ti 5 O 12 has a small volume fluctuation at the time of occlusion and release of lithium ions, it has excellent rapid charge / discharge characteristics, suppresses electrode deterioration, and improves the life of lithium ion secondary batteries. This is preferable.
  • a negative electrode active material containing Si element In the all solid state secondary battery of the present invention, it is also preferable to apply a negative electrode active material containing Si element.
  • a Si negative electrode can occlude more Li ions than current carbon negative electrodes (graphite, acetylene black, etc.). That is, since the amount of Li ion storage per weight increases, the battery capacity can be increased. As a result, there is an advantage that the battery driving time can be extended, and use in a battery for vehicles is expected in the future.
  • the volume change associated with insertion and extraction of Li ions is large. In one example, the volume expansion of the carbon negative electrode is about 1.2 to 1.5 times, and the volume of Si negative electrode is about three times. There is also an example.
  • the durability of the electrode layer is insufficient, and for example, contact shortage is likely to occur, and cycle life (battery life) is shortened.
  • the solid electrolyte composition according to the present invention even in an electrode layer in which such expansion / contraction increases, the high durability (strength) can be exhibited, and the excellent advantages can be exhibited more effectively. is there.
  • the concentration of the negative electrode active material is not particularly limited, but is preferably 10 to 80% by mass, more preferably 20 to 70% by mass in 100% by mass of the solid component in the solid electrolyte composition.
  • said embodiment considered and demonstrated the example which makes a specific solid electrolyte composition contain a positive electrode active material or a negative electrode active material
  • this invention is not limited and interpreted by this.
  • An inorganic solid electrolyte layer may be formed using the solid electrolyte composition according to a preferred embodiment of the present invention in combination with such a commonly used positive electrode material or negative electrode material.
  • carbon fibers such as graphite, carbon black, acetylene black, ketjen black, carbon nanotubes, metal powders, metal fibers, polyphenylene derivatives, and the like can be included.
  • the said negative electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the positive / negative current collector an electron conductor that does not cause a chemical change is preferably used.
  • the current collector of the positive electrode in addition to aluminum, stainless steel, nickel, titanium, etc., the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver. Among them, aluminum and aluminum alloys are preferable. More preferred.
  • the negative electrode current collector aluminum, copper, stainless steel, nickel, and titanium are preferable, and aluminum, copper, and a copper alloy are more preferable.
  • a film sheet is usually used, but a net, a punched one, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 ⁇ m to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • the all-solid-state secondary battery may be manufactured by a conventional method. Specifically, there is a method in which the solid electrolyte composition is applied onto a metal foil serving as a current collector to form a battery electrode sheet having a coating film formed thereon. For example, a composition serving as a positive electrode material is applied onto a metal foil that is a positive electrode current collector and then dried to form a positive electrode layer. Next, the solid electrolyte composition is applied onto the positive electrode sheet for a battery and then dried to form a solid electrolyte layer. Furthermore, after applying the composition used as a negative electrode material on it, it dries and forms a negative electrode layer.
  • a structure of an all-solid-state secondary battery in which a solid electrolyte layer is sandwiched between a positive electrode layer and a negative electrode layer can be obtained by stacking a current collector (metal foil) on the negative electrode side thereon.
  • coating method of said each composition should just follow a conventional method.
  • a drying treatment may be performed after each application of the composition forming the positive electrode active material layer, the composition forming the inorganic solid electrolyte layer (solid electrolyte composition), and the composition forming the negative electrode active material layer.
  • a drying process may be performed.
  • drying temperature is not specifically limited, 30 degreeC or more is preferable and 60 degreeC or more is more preferable.
  • the upper limit is preferably 300 ° C. or lower, and more preferably 250 ° C. or lower.
  • the all solid state secondary battery according to the present invention can be applied to various uses.
  • the application mode is not particularly limited, for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a cellular phone, a cordless phone, a pager, a handy terminal, a portable fax machine, a portable copy.
  • Examples include portable printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, and memory cards.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.
  • a solid electrolyte composition (positive electrode or negative electrode composition) containing an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the Periodic Table.
  • the battery electrode sheet which formed the said solid electrolyte composition on metal foil.
  • An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the inorganic solid electrolyte layer is All-solid-state secondary battery made into the layer comprised with the solid electrolyte composition.
  • the manufacturing method of the electrode sheet for batteries which arrange
  • the manufacturing method of the all-solid-state secondary battery which manufactures an all-solid-state secondary battery via the manufacturing method of the said battery electrode sheet.
  • An all-solid secondary battery refers to a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolyte type secondary battery using a carbonate-based solvent as an electrolyte.
  • this invention presupposes an inorganic all-solid-state secondary battery.
  • the all-solid-state secondary battery is classified into an organic (polymer) all-solid-state secondary battery that uses a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state secondary battery that uses the above LLT, LLZ, or the like. .
  • the application of the polymer compound to the inorganic all-solid secondary battery is not hindered, and the polymer compound can be applied as a binder for the positive electrode active material, the negative electrode active material, and the inorganic solid electrolyte particles.
  • the inorganic solid electrolyte is distinguished from an electrolyte (polymer electrolyte) using the above-described polymer compound as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the above LLT and LLZ.
  • the inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function.
  • a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations is sometimes called an electrolyte, but it is distinguished from the electrolyte as the ion transport material.
  • electrolyte salt or “supporting electrolyte”.
  • the electrolyte salt include LiTFSI (lithium bistrifluoromethanesulfonimide).
  • composition means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.
  • Synthesis Example 2 Synthesis of methylbutylcellulose (P-2) In a 5000 mL three-necked flask equipped with a reflux condenser, a mechanical stirrer, a thermometer, and a dropping funnel, methylcellulose (manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1.8) 80.0 g and dimethylacetamide 2000 mL were added and stirred at room temperature, then 100 g of powdered sodium hydroxide was added and stirred at 60 ° C. for 1 hour. While cooling the reaction solution on a water bath, 80 mL of butyl iodide was slowly added dropwise, and the mixture was further stirred at 50 ° C. for 3 hours.
  • methylcellulose manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1.8
  • the temperature was returned to room temperature, and the reaction solution was poured into 12 L of methanol with vigorous stirring to precipitate a white solid.
  • the white solid was separated by suction filtration, and then washed three times with a large amount of isopropanol.
  • the obtained white solid was dried under reduced pressure at 100 ° C. for 6 hours to obtain 84.0 g of the intended P-2.
  • the weight average molecular weight was 399,000.
  • Synthesis Example 3 Synthesis of methyl octyl cellulose (P-3) 86.0 g of the target P-3 was obtained in the same manner as in Synthesis Example 2 except that butyl iodide was changed to octyl iodide. The weight average molecular weight was 425,000.
  • Synthesis Example 4 Synthesis of methyl stearyl cellulose (P-4) 90.0 g of the target P-4 was obtained in the same manner as in Synthesis Example 2 except that butyl iodide was changed to stearyl iodide. The weight average molecular weight was 463,000.
  • Synthesis Example 5 Synthesis of methylphenylcellulose (P-5) 84.0 g of the target P-5 was obtained in the same manner as in Synthesis Example 2 except that butyl iodide was changed to iodobenzene. The weight average molecular weight was 444,000.
  • Synthesis Example 6 Synthesis of Cellulose Octylate (P-6) In a 5000 mL three-necked flask equipped with a reflux condenser, a mechanical stirrer, a thermometer, and a dropping funnel, 80.0 g of cellulose (manufactured by Nippon Paper Industries Co., Ltd .: KC Flock W400) After adding 1800 mL of dimethylacetamide and stirring at 120 ° C. for 2 hours, 150.0 g of lithium chloride was added, and stirring was further continued for 1 hour.
  • cellulose manufactured by Nippon Paper Industries Co., Ltd .: KC Flock W400
  • Synthesis Example 7 Synthesis of methylcellulose butanoate (P-7) In a 5000 mL three-necked flask equipped with a reflux condenser, a mechanical stirrer, a thermometer, and a dropping funnel, methylcellulose (manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1. 8) After adding 80.0 g, 1000 mL of methylene chloride and 1000 mL of pyridine, stirring at room temperature, 1000 mL of butyric anhydride was slowly added dropwise, and 0.2 g of dimethylaminopyridine (DMAP) was further added, followed by heating at reflux for 3 hours. did.
  • DMAP dimethylaminopyridine
  • the temperature was returned to room temperature, and quenched by adding 200 mL of methanol on an ice bath.
  • the reaction solution was poured into methanol / water (10 L / 10 L) with vigorous stirring to precipitate a white solid.
  • the white solid was filtered off by suction filtration and then washed with a large amount of water three times.
  • the obtained white solid was dried under reduced pressure at 100 ° C. for 6 hours to obtain 78.0 g of the intended P-7.
  • the weight average molecular weight was 582,000.
  • Synthesis Example 8 Synthesis of methylcellulose octanoate (P-8) In a 5000 mL three-necked flask equipped with a reflux condenser, a mechanical stirrer, a thermometer, and a dropping funnel, methylcellulose (manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1. 8) 80.0 g and 1500 mL of pyridine were added and stirred at room temperature, and then 160 mL of n-octanoyl chloride was slowly added dropwise thereto under ice cooling, followed by stirring at 60 ° C. for 6 hours. After the reaction, the temperature was returned to room temperature, and quenched by adding 200 mL of methanol on an ice bath.
  • the reaction solution was poured into 12 L of water with vigorous stirring to precipitate a white solid.
  • the white solid was separated by suction filtration, and then washed with a large amount of methanol three times.
  • the obtained white solid was dried under reduced pressure at 100 ° C. for 6 hours to obtain 93.0 g of the intended P-8.
  • the weight average molecular weight was 603,000.
  • Synthesis Example 10 Synthesis of methylcellulose benzoate (P-10) 82.0 g of the target P-10 was obtained in the same manner as in Synthesis Example 8 except that n-octanoyl chloride was changed to benzoic acid chloride. The weight average molecular weight was 522,000.
  • Synthesis Example 11 Synthesis of Cellulose Ethyl Carbonate (P-11) 110.0 g of the target P-11 was obtained in the same manner as in Synthesis Example 6 except that n-octanoyl chloride was changed to ethyl chloroformate. The weight average molecular weight was 168,000.
  • Synthesis Example 12 Synthesis of methylcellulose-2-ethylhexyl carbonate (P-12) In the same manner as in Synthesis Example 8 except that n-octanoyl chloride was changed to 2-ethylhexyl chloroformate, the target P-12 was changed to 92 0.0 g was obtained. The weight average molecular weight was 233,000.
  • Synthesis Example 13 Synthesis of methylcellulose propyl carbamate (P-13) The same procedure as in Synthesis Example 8 was repeated except that 160 mL of n-octanoyl chloride was changed to 108.8 g of propyl isocyanate, and the target P-13 was 72. 0 g was obtained. The weight average molecular weight was 144,000.
  • Synthesis Examples 14 and 15 Synthesis of Methyl / Ethylcellulose (P-14, P-15) In the same manner as in Synthesis Example 1 except that butyl iodide was changed to methyl iodide or ethyl iodide, the target P- 14, P-15 was obtained. The weight average molecular weight is shown in the table.
  • P-16 trade name Serogen 3H (carboxyethyl cellulose) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was used, and as the P-17, hydroxypropyl cellulose manufactured by Wako Pure Chemical Industries, Ltd. was used.
  • ⁇ About substitution degree> In the three hydroxyl groups on the ⁇ -glucose ring in cellulose, the substitution degree of the substituent B is DS B , and the substitution degree of the substituent C is DS C.
  • the substitution degree is expressed as DS A as the substituent A substituted with a hydrogen atom, and therefore the total of the substitution degrees (DS A + DS B + DS C ) is 3.
  • the total substitution degree of the hydroxyl groups of the cellulose polymer is DS B + DS C.
  • substituent A, substituent B, and substituent C do not correspond to L 2 X 2 , L 3 X 3 , and L 6 X 6 in formula (1).
  • substituent A, the substituent B, and the substituent C are any of L 2 X 2 , L 3 X 3 , and L 6 X 6 in the formula (1), but any of them may mean It is.
  • the substituent A, the substituent B, and the substituent C are each a substituent composed of a combination of a divalent linking group L A , L B , L C and a substituent X A , X B , X C. .
  • P-1 is described in detail in the column of substituents A and B, and “-” is described in the column of substituent C.
  • the molecular weight of the polymer means the weight average molecular weight unless otherwise specified, and the weight average molecular weight in terms of standard polystyrene is measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the value measured under the following conditions is basically used. However, an appropriate eluent may be selected and used depending on the polymer type. (conditions) Column: TOSOH TSKgel Super AWM-H is connected Carrier: 10 mM LiBr / N-methylpyrrolidone
  • Example of production of solid electrolyte sheet The solid electrolyte composition obtained above was applied onto an aluminum foil having a thickness of 20 ⁇ m with an applicator having an arbitrary clearance, and heated at 80 ° C. for 1 hour and further at 110 ° C. for 1 hour to dry the coating solvent. Then, 20-micrometer-thick copper foil was match
  • composition for positive electrode of secondary battery In a planetary mixer (TK Hibismix, manufactured by PRIMIX), 100 parts of the positive electrode active material shown in Table 4 below, 5 parts of acetylene black, solid electrolyte composition 75 obtained above And 270 parts of N-methylpyrrolidone were added and stirred at 40 rpm for 1 hour.
  • TK Hibismix manufactured by PRIMIX
  • the secondary battery positive electrode composition obtained above was applied onto an aluminum foil having a thickness of 20 ⁇ m with an applicator having an arbitrary clearance, and heated at 80 ° C. for 1 hour and further at 110 ° C. for 1 hour. Then, the coating solvent was dried. Then, it heated and pressurized so that it might become arbitrary density using the heat press machine, and the positive electrode sheet for secondary batteries was obtained.
  • the solid electrolyte composition obtained above was applied with an applicator having an arbitrary clearance, and 80 ° C. for 1 hour and further 110 ° C. Heated for hours. Thereafter, the composition for a secondary battery negative electrode obtained above was further applied and heated at 80 ° C. for 1 hour and further at 110 ° C. for 1 hour.
  • a copper foil having a thickness of 20 ⁇ m was combined on the negative electrode layer, and heated and pressurized to an arbitrary density using a heat press machine to obtain a secondary battery electrode sheet.
  • the secondary battery electrode sheet has the configuration of FIG.
  • the film thickness of the positive electrode layer and the negative electrode layer was 80 ⁇ m, and the film thickness of the electrolyte layer was 30 ⁇ m.
  • Other secondary battery electrode sheets were produced in the same manner.
  • Bindability using a sheet before applying the negative electrode current collector copper foil (a state where the solid electrolyte composition or the negative electrode composition is applied and dried) in the solid electrolyte sheet or secondary battery electrode sheet manufacturing process was evaluated.
  • An adhesive tape (cellophane tape ("CT24", manufactured by Nichiban Co., Ltd.)) was applied to the solid electrolyte composition or the negative electrode composition after drying, and the peeled area was visually confirmed when peeled off at a constant speed. .
  • the area ratio of the part that was not peeled was evaluated as follows. A: 90% or more B: 70% or more and less than 90% C: 50% or more and less than 70% D: Less than 50%
  • the solid electrolyte sheet or secondary battery electrode sheet obtained above was cut into a disk shape having a diameter of 14.5 mm and placed in a stainless steel 2032 type coin case incorporating a spacer and a washer to produce a coin battery. From the outside of the coin battery, it was sandwiched between jigs capable of applying pressure between the electrodes, and used for various electrochemical measurements. The pressure between the electrodes was 500 kgf / cm 2 . It calculated
  • 11 is an upper support plate
  • 12 is a lower support plate
  • 13 is a coin battery
  • 14 is a coin case
  • 15 is an electrode sheet (solid electrolyte sheet or secondary battery electrode sheet), and S is a screw.
  • Table 3 shows the measurement results of the electrode binding properties of the solid electrolyte sheet and the ionic conductivity in the pressurized and non-pressurized states.
  • the measurement in the pressurized state is a case where the measurement is performed with the coin battery sandwiched between the jigs, and the measurement in the non-pressurized state indicates that the coin battery is measured as it is.
  • Table 4 shows the measurement results of the electrode binding property of the secondary battery electrode sheet and the ionic conductivity in the pressurized and non-pressurized states.
  • the measurement in the pressurized state is a case where the measurement is performed with the coin battery sandwiched between the jigs, and the measurement in the non-pressurized state indicates that the coin battery is measured as it is.
  • the cell structure represented the structure by describing the solid electrolyte composition which formed each layer, and a positive electrode active material or a negative electrode active material.
  • the solid electrolyte sheet using the solid electrolyte composition of the present invention and the laminated battery are excellent in electrode binding properties and excellent in ion conductivity in a non-pressurized state. . From this, during the handling of the electrode sheet in production, the solid electrolyte layer and the electrode active material layer do not peel off, and the electrochemical contact at the solid interface can be maintained. Is expected to be good. On the other hand, in the comparative example of T-1 not containing the solid electrolyte composition of the present invention and T-2 using polyethylene oxide, the electrode flexibility is inferior and the ionic conductivity in the non-pressurized state is also greatly inferior.
  • a solid electrolyte composition S-15 using ethyl cellulose (P-15) synthesized above was prepared. This was applied onto a metal foil and formed into an electrode sheet. This electrode sheet was fired at 600 ° C. for 1 hour. Thereafter, a test body of an all-solid secondary battery was produced in the same manner as described above.
  • the binding property was a result of “D”
  • the ionic conductivity was 0.15 mS / cm when pressurized, and could not be measured when not pressurized. As a result, it was not possible to measure due to the occurrence of cracks.
  • even if it uses the solid electrolyte composition which used the cellulose for the medium what became the state which does not function as a binder by baking processing does not correspond to the structure of this invention.

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Abstract

　L'invention concerne une pile rechargeable entièrement solide pourvue d'une couche de matière active d'électrode positive, d'une couche de matière active d'électrode négative, et d'une couche d'électrolyte solide inorganique, au moins une couche parmi la couche de matière active d'électrode positive, la couche de matière active d'électrode négative, et la couche d'électrolyte solide inorganique contenant un polymère de cellulose et un électrolyte solide inorganique présentant une conductivité par rapport aux ions d'un métal appartenant au groupe 1 ou 2 du tableau périodique.
PCT/JP2015/059677 2014-03-28 2015-03-27 Pile rechargeable entièrement solide, composition d'électrolyte solide et feuille d'électrode de pile utilisée pour celle-ci, et procédé de fabrication d'une feuille d'électrode de pile et d'une pile rechargeable entièrement solide WO2015147279A1 (fr)

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CN109155414A (zh) * 2016-06-09 2019-01-04 日本瑞翁株式会社 固体电解质电池用粘结剂组合物、及固体电解质电池用浆料组合物
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JP6962249B2 (ja) * 2018-03-22 2021-11-05 トヨタ自動車株式会社 硫化物固体電池
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CN109155414A (zh) * 2016-06-09 2019-01-04 日本瑞翁株式会社 固体电解质电池用粘结剂组合物、及固体电解质电池用浆料组合物
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